+)))))))))))))))))))))))))))))))))))))))))))))))))))))))))))))))))))))), * MCP Application Notes: * * * * 1. Character(s) preceded & followed by these symbols (. -) or (+ ,) * * are super- or subscripted, respectively.

* * EXAMPLES: 42m.3- = 42 cubic meters * * CO+2, = carbon dioxide * * * * 2. All table notes (letters and numbers) have been enclosed in square* * brackets in both the table and below the table. The same is * * true for footnotes. * .))))))))))))))))))))))))))))))))))))))))))))))))))))))))))))))))))))))-

232.1R-94 USE OF NATURAL POZZOLANS IN CONCRETE Reported by ACI Committee 232 Orville R. Werner II,* Chairman J. Floyd Best W. Barry Butler Bayard M. Call Ramon L. Carasquillo James E. Cook Douglas W. Deno Ravindra K. Dhir Bryce A. Ehmke William E. Ellis, Jr. Thomas A. Fox William H. Gehrmann William Halczak Ronald H. Hall G. Terry Harris, Sr.
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Paul J. Tikalsky,* Secretary Harry L. Patterson Terry Patzias* Sandor Popovics D.V. Reddy Harry C. Roof Della M. Roy Mauro J. Scali John M. Scanion Donald L. Schlegel Ava Shypula Peter G. Show Bruce A. Suprenant Samuel S. Tyson Jack W. Weber

Tarif M. Jaber Jim S. Jensen Roy H. Keck Paul Klieger Henry J. Kolbeck Steven H. Kosmatka Ronald L. Larsen Richard J. Majko V. M. Malhotra Larry W. Matejcek Bryant Mather* Richard C. Meininger Richard C. Mielenz* Tarun R. Naik

Members of the Subcommittee who prepared this report.

This state-of-the-art report provides a historical background on the use of natural pozzolans during the past three thousand years, and an overview of the properties of natural pozzolans and their proper use in the production of portland-cement concrete. Natural pozzolans mixed with lime were used in concrete construction long before the invention of portland cement because of their contribution to strength of concrete and mortar. Today, natural pozzolans are used with portland cement not only to contribute to strength, but also for economy and beneficial modification of certain properties of fresh and hardened portland-cement concrete. The report contains information and recommendations concerning the selection and use of natural pozzolans generally conforming to the requirements of ASTM C 618. Topics covered include the effect of natural pozzolans on concrete properties, a discussion of quality control and quality assurance, and guidance regarding handling and use of natural pozzolans in specific applications. References are provided that offer more information on each topic. Keywords: alkali-silica reaction; calcined shale; cement; concrete; concrete strength; diatomaceous earth; lime; natural pozzolan; pozzolan; pozzolanic activity; sulfate attack (on concrete); volcanic ash.
+)))))))))))))))))))))))))))))))))))))))))))))))))))))))))))))))))))))))))), * ACI Committee Reports, Guides, Standard Practices, and * * Commentaries are intended for guidance in designing, planning, * * executing, or inspecting construction and in preparing specifications. * * Reference to these documents shall not be made in the Project Documents.* * If items found in these documents are desired to be part of the * * Project Documents, they should be phrased in mandatory language and * * incorporated in the Project Documents. * .))))))))))))))))))))))))))))))))))))))))))))))))))))))))))))))))))))))))))-

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ACI 232.1R-94 became effective Nov. 11, 1994 Copyright 1994, American Concrete Institute All rights reserved, including rights of reproduction and use in any form or by means, including the making of copies by any photo process, or by any electronic or mechanical device, printed, written, or oral, or recording for sound or visual reproduction or for use in any knowledge or retrieval system or device, unless permission in writing is obtained from the copyright proprietors. CONTENTS Chapter 1--General, p. 232.1R-2 1.1--History 1.2--What is a natural pozzolan? 1.3--Sources of natural pozzolans 1.4--Chemical and mineralogical composition 1.5--Chemical and physical manifestations 1.6--Uses Chapter 2--Effects of natural pozzolan on concrete properties, p. 232.1R-6 2.1--Concrete mixture proportions 2.2--Properties of fresh concrete 2.3--Properties of hardened concrete Chapter 3--Specifications, test methods, quality control, and quality assurance, p. 232.1R-12 3.1--Introduction 3.2--Chemical requirements 3.3--Physical requirements 3.4--General specification provisions 3.5--Methods of sampling and testing 3.6--Quality control and quality assurance Chapter 4--Concrete production with natural pozzolans, p. 232.1R-13 4.1--Storage 4.2--Batching 4.3--Mass concrete Chapter 5--Natural pozzolans in concrete products, p. 232.1R-14 5.1--Concrete masonry units 5.2--Concrete pipes 5.3--Prestressed concrete products Chapter 6--Other uses of natural pozzolans, p. 232.1R-15 6.1--Grouts and mortars 6.2--Controlled low-strength materials Chapter 7--References, p. 232.1R-16 7.1--Specified and/or recommended references 7.2--Cited references CHAPTER 1--GENERAL 1.1--History Lime and limestone are prehistoric materials that are among the oldest

used by mankind for construction purposes. Structures built of limestone include the pyramids of Egypt. Long before the invention of portland cement in 1824, mortars and concretes were in use for construction throughout the world, as mixtures of fillers and raw or heat-treated lime. The next oldest material was a natural pozzolan, used in combination with lime. The pozzolan was volcanic ash produced from two violent volcanic eruptions in the Mediterranean: One, sometime between 1600 and 1500 BC on the Aegean Island of Thera, now called Santorin, Greece, and another, in 79 AD at Mt. Vesuvius on the bay of Naples, Italy. Both are volcanic ashes or pumicites consisting of almost 80 volcanic glass (pumice and obsidian). According to the Roman Engineer Marcus Vitruvius Pollio (Vitruvius Pollio), who lived in the first century BC, the cements made by the Greeks and the Romans were of superior durability, because "neither waves could break, nor water dissolve" the concrete. In describing the building techniques of masonry construction, he indicated that the Romans developed superior practices of their own, from the techniques of the Etruscans and the Greeks. The Greek masons discovered pozzolan-lime mixtures sometime between 700 and 600 BC, and later passed their use in concrete along to the Romans about 150 BC. During the 600 years of Roman domination, the Romans discovered and developed a variety of pozzolans throughout their empire (Kirby et al. 1956). 1.2--What is a natural pozzolan? Pozzolan is defined in ACI 116R as: "a siliceous or siliceous and aluminous material, which in itself possesses little or no cementitious value but will, in finely divided form and in the presence of moisture, chemically react with calcium hydroxide at ordinary temperatures to form compounds possessing cementitious properties. Natural pozzolan is defined as: "either a raw or calcined natural material that has pozzolanic properties (e.g., volcanic ash or pumicite, opaline chert and shales, tuffs, and some diatomaceous earths). ASTM C 618 covers fly ash and natural pozzolan for use as a mineral admixture in concrete. The natural pozzolans in the raw or calcined state are designated as Class N pozzolans, and are described in the specifications as: "Raw or calcined natural pozzolans that comply with the applicable requirements for the class as given herein, such as some diatomaceous earth; opaline cherts and shales; tuffs and volcanic ashes or pumicites, any of which may or may not be processed by calcination; and various materials requiring calcination to induce satisfactory properties, such as clays and shales. Similar materials of volcanic origin are found in Europe where they have been used as an ingredient of hydraulic-cement concrete for the past two centuries. 1.3--Sources of natural pozzolans Following is a list of some natural pozzolans found in Greece, Italy, France, Germany, Turkey, Spain, the United States, Soviet Union, China, Mexico, Japan, and India. 1. Santorin earth is a natural deposit of volcanic ash of dolcitic

composition on the island of Thera (Santorin), which came out of an active volcano at about 1600-1500 BC after a tremendous explosive eruption (Marinatos 1972). 2. Pozzuolana is a deposit of pumice ash or tuff of trachytic composition found near Naples and Segni in Italy. This is also a product of an explosive volcanic eruption in 79 A.D. at Mount Vesuvius, which engulfed Herculaneum, Pompeii, and other towns along the bay of Naples. The deposit near Pozzuoli was the source of the name of pozzolan given to all materials having similar properties. Similar tuffs of lower silica content have been worked for centuries and are found in the vicinity of Rome. 3. Rheinish trass, a natural pozzolan of volcanic origin (TRB 119), is well known since the Roman times. The material is a trachytic tuff that differs from place to place and is found in the Valley of the Rhine River in Germany. Similar tuffs have been used in Bavaria. 4. Gaize, a pozzolan in France that is not of volcanic origin, but a porous sedimentary rock consisting mainly of opal. 5. Worldwide sources--In the Soviet Union and Japan, pozzolanic materials have been investigated and used in mixtures with portland cement since the 1930s. Similarly, China, India, Turkey, Brazil, and Mexico are using substantial amounts of natural pozzolans for production of blended cements to meet the increasing demand for cement. Kaolin clay form along the Parana River near Jupia Dam in Brazil was calcined and ground for use in construction of four major dams. The cost of the manufactured pozzolan was approximately one third that of portland cement (Saad, Andrade, and Paulon 1981). 6. In the United States, volcanic tuffs and pumicites, diatomaceous earth, and opaline shales are found principally west of the Mississippi River in Oklahoma, Nevada, Arizona, and California. Natural pozzolans were investigated in this country by Bates and colleagues as early as 1908 (Bates, Phillips, and Wig 1912) and later by Price, Meissner, Mielenz, Davis, and others. It was shown by them that concretes containing pozzolanic materials exhibited certain desirable properties. According to Price (1975), an example of the first large use of portland-pozzolan cement is the Los Angeles aqueduct in 1910 to 1912. It was composed of equal parts of portland cement and a rhyolite pumicite. In the 1920s and 1930s, natural pozzolans were used as mineral admixtures in concrete for the construction of certain dams and other structures then being constructed by the Los Angeles Flood Control District. The California Division of Highways used a specially made portland-pozzolan cement in several structures (bridges) because of its proven resistance to sulfate attack from sea water, and its lower heat of hydration (Davis 1950). In 1935, a portland-pozzolan cement was used in the construction of Bonneville Dam, and in 1942, a pozzolan was added at the concrete mixer for construction of Friant Dam (Davis 1950). The studies of natural pozzolans by the Bureau of Reclamation in the 1930s and 1940s encouraged the use of these materials for the control of the heat of hydration, and alkali-silica reaction, of concrete in large dams. Siliceous shales of the Monterey Formation in Southern California have been mined for natural pozzolan produced commercially and used extensively in the surrounding areas. According to Price (1975), sources of natural pozzolan that do not require calcining to make them active are located mainly west of the Mississippi River. Generally the pozzolanic deposit was in the vicinity of the particular project and the amount required was sufficiently large to support mining and processing costs. The deposit was usually abandoned at the completion of the project.

Meissner (1950) reported that the Santa Cruz Portland Cement Co. had been producing a portland-pozzolan cement containing 25 percent interground calcined Monterey shale during the 1930s and 1940s. This cement was used in 1932 by the California Division of Highways in several structures including the Golden Gate Bridge and the San Francisco-Oakland Bay Bridge. Another pozzolanic cement was used in 1935 for the construction of the Bonneville Dam spillway on the lower Columbia River. This material was produced by the Pacific Portland Cement Company by integrinding 25 percent calcined pozzolan. In 1940 to 1942, the Friant Dam on the San Joaquin River California was built by the Bureau of Reclamation with a portland cement-pozzolan combination. The pozzolan was a naturally fine pumicite (raw rhyolitic pumicite), which was batched separately at the concrete mixer at the rate of 20 percent by weight of cement. This pozzolan was obtained from a deposit along the San Joaquin River near Friant. During the 1960s and early 1970s, natural pozzolan was used at the rate of 41 kg/m.3- (70 lb/yd.3-) in nearly all of the concrete in the California State Water Project, including lining of the California Aqueduct (Tuthill 1967; Adams 1968; Tuthill and Adams 1972). This was the most extensive use of a natural pozzolan in a project in U.S. history. Requirements on this pozzolan exceeded those of ASTM to assure that only the highest quality of pozzolan would be used. 1.4--Chemical and mineralogical composition The properties of natural pozzolans vary considerably, depending on their origin. This is caused by the variable proportions of the active materials, and the mineralogical and physical characteristics. Most natural pozzolans contain substantial amounts of constituents other than silica, such as alumina and iron oxide, and alkalies, which will also react with calcium hydroxide and alkalies (sodium and potassium) to form more complex compounds. But the molecular structure of the silica is very important as well as the amount present in determining pozzolanic activity. There is no clear line of separation between siliceous materials that are considered as pozzolans and those that are not. Generally, amorphous silica reacts with calcium hydroxide and alkalies more rapidly than does silica in the crystalline form (quartz). As is the case with all solid state chemical reactions, the larger the particles (the lower the surface area) the less rapid the rate of reaction. Thus, the chemical composition of a pozzolan does not clearly determine its ability to combine with calcium hydroxide and alkalies. Volcanic glasses and zeolitic tuffs, when mixed with lime, produce calcium silicate hydrates (CSH) as well as hydrated calcium aluminates and calcium aluminosilicates. These materials were proved to be good pozzolans long ago. Clays and shales are not pozzolanic or only weakly so, since clay minerals do not readily react with lime unless their crystalline structure is destroyed by heat. Italian researchers who have studied the volcanic glasses and their relationship to their pozzolanic activity believe that "the reactive glass originates from explosive volcanic eruptions" like the ones from the volcanos of Thera and Mount Vesuvius, which produced the natural pozzolans with unaltered aluminosilicate glass as their major component (Malquori 1960). Both of them are pumicites, one-third of which is in the amorphous state (glass), and are highly reactive with lime and alkalies even at normal temperatures. Mehta (1987) classifies natural pozzolans in four categories on the basis of the principal lime-reactive constituent present: (1) unaltered volcanic glass; (2) volcanic tuff; (3) calcined clay or shale; and (4) raw or calcined opaline silica. This classification is not readily applicable to pozzolans of volcanic origin (Categories 1 and 2) because volcanic tuffs commonly include unaltered siliceous glass. This is the sole or main source of pozzolanic activity in siliceous glass, opal, zeolites, or clay minerals,

the activity of the last two being enhanced by calcination. A classification of natural pozzolans based on the identity of the pozzolanic constituents was devised by Mielenz et al. (1950). Substances that are pozzolanic or whose pozzolanic activity can be induced by calcination were identified as (1) volcanic glass, (2) opal, (3) clays, (4) zeolites, and (5) hydrated oxides of aluminum. Six activity types were proposed, as follows: Activity Activity Activity Activity Activity Activity Activity Activity Activity Activity Type Type Type Type Type Type Type Type Type Type 1: Volcanic glass 2: Opal 3: Clay 3a: Kaolinite-type clay 3b: Montmorillonite-type clay 3c: Illite-type clay 3d: Mixed clay with vermiculite 4: Zeolite 5: Hydrated oxides of aluminum 6: Nonpozzolan

In Table 1, the chemical and mineralogical composition is given for some of the well-known pozzolans.

1.5--Chemical and physical manifestations When a mixture of portland cement and a pozzolan reacts, the pozzolanic

reaction progresses like an acid-base reaction of lime and alkalies with oxides (SiO+2, + Al+2,O+3, + Fe+2,O+3,) of the pozzolan. Two things happen: first, there is a gradual decrease in the amount of free calcium hydroxide with time, and second, there is an increasing formation of CSH and calcium aluminosilicates that are similar to the products of hydration of portland cement (Fig. 1). According to Lea (1971), the partial replacement of portland cement by pozzolan of high SiO+2,/R+2,O+3, ratio has been found to increase the resistance of concrete to sulfate and seawater attack (R+2,O+3, is approximately the summation of the Al+2,O3 and Fe+2,O+3, contents). This is in part attributable to the removal of free calcium hydroxide formed in the hydration of portland cements by combination with the pozzolan. The end result will be that the paste will contain less calcium hydroxide and more CSH and other products of low porosity. Research on the hydration of blended cements made with natural pozzolans of volcanic origin (Santorin earth, Pozzuolana) has confirmed that rather than the chemical manifestation, the physical manifestation of the pozzolanic reaction that involves pore refinement of the cement paste is probably more important for the enhancement of chemical durability and mechanical strength (Mehta 1987). The shape, fineness, particle size distribution, density, and composition of natural pozzolan particles influence the properties of freshly mixed unhardened concrete, and the strength development of hardened concrete. Most natural pozzolans tend to increase the water requirement in the normal consistency test, as a result of their microporous character and high surface area. When properly employed as an ingredient of portland-pozzolan cements or as admixtures to portland-cement concrete, pozzolans can improve the performance of both fresh and hardened concrete. 1.6--Uses Pozzolans of natural origin have been used in mass concrete on several large projects in the United States and where they are locally available, they are used in concrete construction and manufacture of concrete products. Such uses of pozzolans of natural origin are more widespread in Europe than in the United States. In modern times, natural pozzolans have been used in concrete much the same as fly ash is used in concrete. The natural pozzolans may be used as partial replacements for portland cement or in addition to portland cement. During archaeological excavations in the 1970s at the ancient city of Camiros on the Island of Rhodes, Greece, an ancient water-storage tank was found having a capacity of 600 cubic meters. Built in about 600 BC, it was used until 300 BC when a new hydraulic system with an underground water tank was constructed to the south of a Doric Stoa. For almost three millennia this water tank has remained in very good condition, according to Efstathiadis (1978). Table 2--Pozzolans and structures utilizing them (Elfert 1974)
)))))))))))))))))))))))))))0))))))))))))))))0)))))))))))))))))))))))))))))))) Name * Date * Type of pozzolan *Completed * )))))))))))))))))))))))))))3))))))))))))))))3)))))))))))))))))))))))))))))))) Arrowrock Dam * 1915 * Granite* * 1915 * Siliceous silt* Lahontan Dam Elephant Butte Dam * 1916 * Sandstone* Friant Dam * 1942 * Pumicite Hoover Dam * * (repair of tunnel spillway* 1942 * Fly ash Altus Dam * 1945 * Pumicite Davis Dam * 1950 * Calcined opaline shale Hungry Horse Dam * 1953 * Fly ash

* 1953 * Calcined oil-impregnated * * diatomaceous shale Cachuma Dam * 1953 * Do * * Portland-pozzolan cement Trenton Dam * 1953 * (calcined quartzose silt * * pozzolan) Canyon Ferry Dam * 1954 * Fly ash Tecolote Tunnel * 1957 * Calcined oil-impregnated * * diatomaceous shale Monticello Dam * 1957 * Calcined diatomaceous clay Palisades Dam * 1958 * Fly ash Twitchell Dam * 1958 * Calcined diatomaceous clay Flaming Gorge Dam * 1963 * Calcined montmorillonite shale Glen Canyon Dam * 1964 * Pumice Yellowtail Dam * 1966 * Fly ash San Luis Drain--Central * * Valley Project (three * 1971 * Fly ash separate contracts) * * Initial construction for * 1972 * Fly ash Pueblo Dam * * Grand Coulee Third * * Fly ash Powerplant and Forebay * * Dam * 1974 (est) * Pueblo Dam * 1975 (est) * Fly ash * During past * Miscellaneous small pipe contracts (use of pozzolan* 20 years * Fly ash and other pozzolans requested by pipe * * manufacturer) * * )))))))))))))))))))))))))))2))))))))))))))))2))))))))))))))))))))))))))))))))

Glenn Anne Dam

* By present standards, these materials have very little pozzolanic activity. Examination of the materials used for this structure revealed that the concrete blocks and the mortar used were made out of a mixture of lime, Santorin earth, fine sand (2 mm size) and siliceous aggregates with size ranging between 2 and 20 mm (0.08 and 0.75in.). The fresh concrete was poured into wooden sidewall molds at the correct water-cement ratio, for proper workability and watertightness of the structure. The compressive strength of a 20 cm (0.75 in.) cubic specimen was found to be 12 MPa (1700 psi). Mortars like this were known to have a composition of 6 parts by volume of Santorin earth, 2 parts by volume of lime, and 1 part by volume of fine sand. These mortars were used as the first hydraulic cements in aqueducts, bridges, sewers, and structures of all kinds. Some of these structures are still standing along the coasts of Italy, Greece, France, Spain, and in harbors of the Mediterranean Sea. Many were built by the Greeks and Romans over 2000 years ago. Examples of such structures are the Roman aqueducts, the Suez Canal in Egypt built in 1860 (Luce 1969), the Corinthian Canal in 1880, the sea walls and marine structures in the islands of the Aegean Sea, in Syros, Piraeus, Nauplion, etc., and the harbors of Alexandria in Egypt, and in Fiume, Pola Spalato, Zara on the Adriatic Sea, and Constanta (Romania) on the Black Sea. All these structures provide sufficient evidence of the durability of pozzolan-lime cement under conditions of mild weathering exposure. Roman monuments in many parts of Europe are in use today, standing as a tribute to the performance of lime-pozzolan mortars (Lea 1971). According to Mielenz, Witte, and Glantz (1950), the U.S. Bureau of Reclamation undertook in 1933 an intensive study on utilization of natural pozzolans for the purpose of controlling the heat of hydration of concrete for large dams and other concrete benefits. Several investigations revealed

the effect of calcination of more than 200 prospective natural pozzolans upon their properties and performance in concrete. The following properties were reported: 1. 2. 3. Mineralogical and chemical composition. Pozzolanic activity, water requirement, and strength. Expansion due to alkali-silica reactivity.

All the tests were performed during the period of 1933 to 1949 and are reported in their paper (Mielenz, Witte, and Glantz 1950). The authors concluded that calcination of clayey materials was essential to develop satisfactory pozzolanic activity and the response to heat treatment varied with the type of clay minerals present. Many natural pozzolans can be used in the raw state. If moist, they require drying and they usually require grinding before use. The best natural pozzolans owed their activity to volcanic glass with 70 to 73 percent SiO+2, content, and 40 to 100 percent rhyolitic glass. In a recent paper (Mielenz 1983), the history and background on mineral admixtures is given along with the use of natural pozzolans (raw and calcined). Elfert (1974) describes the experiences of the Bureau of Reclamation in the use of large quantities of fly ash and natural pozzolans in the western United States. Table 2 lists the types of pozzolans and the various structures in which these materials have been used. Today, mixtures of portland cement and pozzolan, as covered by ASTM C 595, are used in concrete construction for economic reasons, to help alleviate the energy crisis and to achieve specific technical benefits. CHAPTER 2--EFFECTS OF NATURAL POZZOLAN ON CONCRETE PROPERTIES

2.1--Concrete mixture proportions The most effective method for evaluating the performance of a concrete containing a natural pozzolan and establishing proper mixture proportions for a specific application is by use of a trial batch and testing program. Because some natural pozzolans exceed the performance of others and concrete requirements differ, optimum proportions for a given combination of pozzolan and portland cement cannot be predicted. In cases where a natural pozzolan is used as a replacement for part of the portland cement, either the mass or the solid volume of the pozzolan used in the proportioned mixture will be equal to that of the portland cement that it replaces. However, the mass of natural pozzolan employed may be greater if the concrete is proportioned for optimum properties and maximum economy. The additional mass of natural pozzolan should be regarded as a separate ingredient in concrete and not as a cement replacement. Proportioning techniques involving the use of a finely divided mineral admixture are basically the same as those used in proportioning concrete that does not include such an admixture. Methods for selecting proportions for concrete mixtures are given in ACI 211.1. Specific procedures for proportioning mixtures containing pozzolans were developed by Lovewell and Hyland (1974). When finely divided mineral admixtures are used in significant proportions, as is customary with pozzolans, their solid volume must be taken into account. Since finely divided mineral admixtures have approximately the same fineness as portland cement, they should usually be regarded as part of the cement paste matrix in determining the percentages of fine and coarse aggregate. The effect of the natural pozzolan on the mixing water requirement should also be known. Some finely divided mineral admixtures cause a major

increase in water requirement, others have little or no effect on water requirement, and still others typically reduce the water requirement of concrete in which they are used (Mather 1958). In general, relatively chemically inert finely divided mineral admixtures have no direct effect on the required amount of portland cement in the concrete mixture other than the fact that they may increase or decrease the total water requirement of the concrete, thereby making necessary an adjustment in the cement content. Natural pozzolans not only affect the water requirement of the concrete and the cement content, but, because of their properties, they are often considered as part of the cementing material (U.S. Bureau of Reclamation 1975). They are usually used in the range of 15 to 35 percent by mass of the total cementitious material in the concrete, depending on the purpose for which the concrete is to be employed and the specifications for the work. 2.2--Properties of fresh concrete Where the available concrete aggregates are deficient in the finer particle sizes, particularly material passing the 75-um (No. 200) sieve, the use of a finely divided mineral admixture can reduce bleeding and segregation and increase the strength of concrete by supplying those fines missing from the aggregate (ACI 211.1). When an appropriate quantity of mineral admixture is used to correct such grading deficiencies, no increase in total water content of the concrete is required to achieve a given consistency. Drying shrinkage and absorption of the hardened concrete are not greatly affected. However, a favorable particle shape and a satisfactory fineness of the mineral admixture are necessary qualities if a low water content is to be achieved without use of a water-reducing admixture. For example, coarse pozzolan of poor particle shape, such as finely divided pumicites, may require an increase in water content of the concrete for a given slump. This may contribute to increased bleeding and segregation of the fresh concrete. The use of finely divided mineral admixtures having pozzolanic properties can provide a major economic benefit in that the use of these materials permits a reduction in the amount of portland cement in the mixture. For example, Waugh (1963) reported that the U.S. Army Corps of Engineers had experienced a major economic benefit through the use of natural pozzolan although, aside from a reduction in water requirement, other technical benefits had not been spectacular. When the ratio of surface area of solids to volume of water is low, the rate of bleeding is relatively high. Moreover, most of the bleeding does not appear at the surface; the aggregate particles settle for a short period until they establish point-to-point contacts that prevent further settlement. The watery paste continues to bleed within the pockets defined by aggregate particles leaving water-filled spaces at the undersides of the particles. Thus, with mixtures having the characteristics just discussed, bleeding tends to reduce homogeneity of the concrete. In extreme cases, the lack of homogeneity is manifested by open fissures under the aggregate particles large enough to be easily visible to the unaided eye in a cross section of the concrete. This lack of bond between paste and aggregate reduces the potential strength of concrete and increases permeability and absorption. These undesirable effects can be reduced by increasing the ratio of surface area of solids to volume of water in the paste. This generally increases the stiffness of the paste and at a given slump, affects a wider separation of the aggregate particles in the concrete. The ratio of surface area of solids to volume of water may be increased by increasing the amount of cement (lowering the water-cement ratio of the paste) or by adding a suitable mineral admixture. Although under some circumstances the addition of pozzolans lowers the amount of water and air voids in concrete, such admixtures should not be

regarded as void fillers. A mixture of cement, natural pozzolan, and water forms a soft, plastic paste that envelops the aggregate particles and, in the course of the mixing process, separates them. The natural pozzolan functions to increase the paste content of the mixture and thereby its capacity for plastic deformation. It is desirable to select a natural pozzolan having favorable physical characteristics. The admixture should be such that the paste will contain a maximum proportion of solid matter and a minimum proportion of water. This requires that the mineral particles do not have unfavorable shapes and that the surface area is not too high. For example, bentonite and hydrated lime have surface areas considerably higher than those of cement. The high water demand of these materials creates unfavorable economics by limiting the use of these minerals to small percentages in order to provide characteristics that are not attainable with conventional concrete mixture proportions.

2.3--Properties of hardened concrete Concrete containing a pozzolan typically provides lower permeability, reduced heat of hydration, reduced alkali-aggregate expansion, higher strengths at later ages, and increased resistance to attack from sulfates in seawater or from other sources. Mather (1982) established that the quality of a pozzolan from the standpoint of sulfate resistance is highest in highly siliceous natural pozzolans, silica fume, and Class F fly ashes.

2.3.1 Strength--The effect of a natural pozzolan on the strength of concrete varies markedly with the properties of the particular pozzolan and with the characteristics of the concrete mixture in which it is used. The strength of lean mixtures may be increased and the strength of rich mixtures may be decreased with the use of natural pozzolans. The strength development is a function of the chemical interaction between the natural pozzolan and the portland cement during hydration. For example, materials that are relatively low in chemical activity generally increase the strength of lean mixtures and decrease the strength of rich mixtures. On the other hand, cementitious material and pozzolans contribute to strength not only because of their physical character, but also by reason of their chemical composition. When pozzolanic materials are used to replace cement on an equal volume basis, early strengths may be reduced. These early strengths can be increased by substituting the pozzolanic material for the cement on an equal mass basis or a volumetric amount greater than one-to-one for the cement replaced, provided water content is not increased excessively. It has been shown in Europe and the U.S. that the intergrinding of pozzolans with portland cement clinker in the production of composite or blended cements improves their contribution to strength. Typical results from an investigation of the effect of curing time on the compressive strength of ASTM C 109 mortar cubes, made with portland-pozzolan cements containing 10, 20, and 30 percent Santorin earth, are shown in Fig. 2 and 3 by Mehta (1987). It is clear that the contribution of the pozzolan to strength development occurs sometime after 7 days of hydration. At 28 days the 10 percent Santorin-earth cement compressive strength was higher than the reference portland cement, at 90 days the 10 and 20 percent Santorin-earth cement strengths were higher than the reference portland cement, and at 1 year the 30 percent pozzolan cement was similar to the reference portland cement as shown in Fig. 4. Similar results were reported by Massazza and Costa (1979) on the effect of substituting varying proportions of portland cement with an Italian pozzolan. Fig. 5 compares the strength development of fly ash and a natural pozzolan with the strength of the control concrete. The graph illustrates the typical relationships of lower strengths at early ages and higher strengths at later ages for fly ash concrete when compared to other pozzolans

2.3.2 Sulfate resistance--Use of natural pozzolans with portland cement in concrete generally increases resistance to aggressive attack by seawater, sulfate-bearing soil solutions, and natural acid waters. The relative improvement is greater for concrete with low cement content. The use of a pozzolan with sulfate-resisting portland cements may not increase sulfate resistance and, if chemically active aluminum compounds are present in the pozzolan, a reduction in sulfate resistance of the concrete may result. In a series of tests of 20 cements and blends of Type I with Class F fly ash, Santorin earth, and silica fume using ASTM C 1012, it was found (Patzias 1987) that blended cements manufactured using highly siliceous natural or artificial pozzolans, slags, or silica fume perform better in sulfate environments than ordinary portland cements having the same C3A content as calculated by the Bogue method (Fig. 6). A research program of the Bureau of Reclamation that extended over a period of more than 20 years has clarified many of the claims made for pozzolan's contribution to sulfate resistance (Elfert 1974). Fig. 7 shows an attempt to quantify the benefits derived from various pozzolans in tests extending over a period of 24 years. Massazza and Costa (1979) studied the effect of substituting portland cement with 10, 30, and 40 percent of an Italian pozzolana on the expansion of 1:3 mortar prisms stored for more than 5 years in 1 percent MgSO+4, solution, as shown in Fig. 8. The authors attributed the results to the reduced content of calcium hydroxide and to lower permeability.

2.3.3 Temperature rise--At a given cement content, the use of chemically inert materials has little or no effect on the temperature rise of concrete in place. Pozzolans have been used in mass concrete of low cement content to reduce the temperature rise of concrete as compared to a comparable concrete mixture containing portland cement as the only cementing material. Massazza and Costa (1979) showed in Fig. 9 that the addition of the Italian pozzolan to a portland cement reduced the heat of hydration, although not in direct proportion to the amount of cement replaced. The reduction was smaller, because of some evolution of heat during the pozzolanic reaction. Similarly, Nicolaidis (1957) found that the 7-day heat of hydration of a Greek portland-pozzolan cement with 20 percent cement replacement by Santorin earth was reduced by 9 cal/g, compared to portland cement only. In the construction of mass concrete structures, where the risk of thermal cracking can be a major problem, natural pozzolans have been extensively used in the U.S. From 1910 through 1912, they were used in the construction of the Los Angeles Aqueduct, and later in the construction of the San Francisco Bay and Golden Gate bridges and in the Friant, Bonneville, Davis, Glen Canyon, Flaming Gorge, Wana-pum, and John Day dams. (Davis 1950; Mielenz 1983). Fig. 10 shows the beneficial effects of a fly ash and a natural pozzolan in reducing the temperature rise of mass concrete. The rate of heat development closely parallels the rate of strength development since both are functions of the same chemical reactions. The slower rate of heat development with pozzolans beyond 28 days permits more economic removal of heat than with comparable non-pozzolan concrete (Elfert 1974). 2.3.4 Expansion caused by alkali-silica reaction--It has been reported that almost any pozzolan, when used in sufficient quantity, is capable of preventing excessive expansion resulting from alkali-silica reaction.

However, the use of too small a proportion of pozzolan may actually increase detrimental effects of the alkali-silica reaction. The alkali-silica reaction involves the interaction of hydroxyl ions associated with alkalies in portland cement with certain siliceous constituents of the aggregates in concrete. Products of the reaction can cause excessive expansion, cracking, and general deterioration of the concrete. The term "alkalies" refers to the sodium and potassium hydroxides present in cement in relatively small proportions expressed as sodium oxide (sum of the percentage of Na+2,O and 0.658 times the percentage of K+2,O). When this particular type of distress of concrete was first described by Stanton in 1940, the only apparent remedies were the use of portland cement of low-alkali content (0.60 percent or less computed as Na+2,O) or the avoidance of reactive aggregates. The evaluation of long-time performance of test pavements indicates that pozzolans can be beneficial in reducing or eliminating map cracking and expansion resulting from this reaction.

Many investigators have observed that natural pozzolans are usually more efficient than fly ash in controlling the alkali-silica reaction. Pepper and Mather (1959) found that the percentage by solid volume of the pozzolan needed to replace portland cement for adequate reduction of expansion varied from 20 percent with diatomite, 20 to 30 percent with calcined shale, to 40 to 50 percent with fly ash. In the case of a volcanic glass, only 30 to 35 percent cement replacement was needed to meet the requirements of ASTM C 441. Similarly, the results of an investigation by Mehta (1987) showed that a portland cement with 1.0 percent equivalent Na+2,O blended with 20 or 30 percent Santorin earth was quite satisfactory to control the alkali-silica expansion, as shown in Fig. 11. Fig. 12 shows the effectiveness of several types of pozzolan in reducing alkali-aggregate expansion. Although low-alkali cement is satisfactory for use with most reactive aggregates, there are some aggregates that require the additional control provided by pozzolans. Table 3--Relative Depth of Penetration of Water into Hydrated Cement Pastes (Mehta 1987)
))))))))))))))0))))))))))))))))))))))))))))))))))))))))))))))))))))))))))))) * Depth of penetration /))))))))))0))))))))))))))))0))))))))))))))))0)))))))))))))))) Hydration age* Portland* 10 percent * 20 percent * 30 percent * cement * Santorin earth *Santorian earth * Santorin earth ))))))))))))))3))))))))))3))))))))))))))))3))))))))))))))))3)))))))))))))))) 28 days * 26 * 24 * 25 * 25

* 25 * 23 * 23 * 22 * 25 * 23 * 18 * 15 ))))))))))))))2))))))))))2))))))))))))))))2))))))))))))))))2))))))))))))))))

90 days 1 year

2.3.5 Permeability--Most work on permeability of concrete containing finely divided mineral admixtures has been accomplished with pozzolans. Certain pozzolans are more effective than others in reducing permeability of concrete at early ages. However, under most conditions of service, the permeability of concrete containing any pozzolan is markedly reduced at later ages. Davis (1950) concluded that in mass concrete, the use of a moderate to high proportion of a suitable pozzolan results in a degree of watertightness not otherwise obtainable. Part of the action of pozzolans in reducing permeability of concrete can be attributed to decreased segregation and bleeding and to a reduction of water requirement. Mehta (1981) made a pore-size distribution analysis with mercury intrusion porosimetry on 28-day, 90-day, and 1-year old pastes containing Santorin earth and portland cement. The data showing the effects of the age of hydration and amount of pozzolan present in the cement paste on a 3-hr water-penetrating test are given in Table 3. 2.3.6 Freezing and thawing resistance--Of the finely divided mineral admixtures, pozzolans have received the most attention regarding their effect on freezing and thawing resistance of concrete. The effect of pozzolans on resistance of concrete to freezing and thawing and to the action of deicing chemicals during freezing depends on the proportioning of the concrete, the strength of the concrete, moisture condition of the concrete, and adequacy of the air-void system at the time of exposure (Lovewell 1971).

Generally, the use of a finely divided mineral admixture requires a higher proportion of air-entraining admixture to produce a given air content than that required by a comparable concrete not containing a finely divided mineral admixture. The proportion of air-entraining admixture required may vary considerably among different sources and types of finely divided mineral admixtures. Finely ground pozzolans containing carbon residue tend to reduce the amount of entrained air in a concrete mixture, and therefore may require

a higher dosage of air-entraining admixture to obtain a given amount of entrained air or the desired air-void spacing factor. From the work of the Bureau of Reclamation on the effect of pozzolans in freezing and thawing durability of concrete, it is clear that the curing conditions play a very important role, as shown in Fig. 13. 2.3.7 Drying shrinkage--The drying shrinkage of products made with portland-pozzolan cements is dependent on the hydration products and water demand of the mixtures. Tests should be conducted to determine the drying shrinkage of natural pozzolan and portland cement combinations to determine the properties for a particular project. Many researchers have observed that the cracking tendency resulting from drying shrinkage in concrete containing pozzolans is less than that in corresponding concretes without pozzolans. Massazza and Costa (1979) compared the drying shrinkage of a portland cement and a portland-pozzolan cement with an Italian pozzolana and found a difference of 943 to 890 m/m. Mehta (1981) found that the drying shrinkage of concretes made with blended cements containing 10, 20, and 30 percent Santorin earth was not significantly different from that of the concrete containing the reference portland cement, as shown in Fig. 14. CHAPTER 3--SPECIFICATIONS, TEST METHODS, QUALITY CONTROL, AND QUALITY ASSURANCE 3.1--Introduction The ASTM specification for fly ash and natural pozzolan is ASTM C 618 and the standard test methods are in ASTM C 311. These standards are under the jurisdiction of ASTM Committee C-9. ASTM C 618 was originally published in 1968 to combine and replace C 350 on fly ash and C 402 on other pozzolans for use as mineral admixtures. Method C 311 for sampling and testing was published originally in 1953. 3.2--Chemical requirements Early studies sought to relate pozzolan performance with chemical analysis for silica, alumina, or iron oxide, but had little success. Today many but not all specifications have a minimum requirement for the sum of the oxide SO+2, + A1+2,O+3, + Fe+2,O+3,. The intent is to assure that sufficient potentially reactive constituents are present. ASTM C 618 requires a minimum of 70 percent for the sum of these oxides for Class N pozzolan, 10.0 percent maximum loss on ignition, 4.0 percent maximum SO+3,, and 3.0 percent maximum moisture content. 3.3--Physical requirements Pozzolan fineness is controlled in most cases by limiting the amount retained on the 45-m (No. 325) sieve by wet sieving. Reactivity has been found to be related directly to the quantity passing this sieve, since the coarser particles generally do not react in a reasonable time in concrete. ASTM C 618 limits the amount retained to 34 percent for natural pozzolans. Some specifications use specific surface by air-permeability fineness methods to control fineness; ASTM C 618 does not. The strength activity index with portland cement is considered only as an indicator of reactivity and does not measure the compressive strength of concrete containing the pozzolan. It provides no information on the optimum proportion of pozzolan for use in concrete. Other specified and optional

requirements relating to physical properties include: 1. Water requirement of the mortar mixed to check the strength activity index, to assure that the pozzolan does not cause a large increase in mixing water demand. 2. Soundness is determined by measuring autoclave expansion or contraction of a paste made with 25 parts by mass of the pozzolan and 100 parts by mass of portland cement. A length change of 0.8 percent is the maximum allowed by ASTM C 618. It is specified that if the pozzolan will constitute more than 20 percent of the cementitious material in the proposed concrete, the paste used for autoclave testing shall contain the anticipated percentage of pozzolan. The test protects against the delayed expansion that could occur if sufficient amounts of MgO are present in the concrete as periclase, or CaO is present as hard-burned free lime. 3. Variability limits are given in ASTM C 618. Limits are specified for a pozzolan to keep the variation of specific gravity and fineness within practical limits for shipments over a period of time. Also, for pozzolan used in air-entrained concrete there is an optional limit on the permitted variation of air-entraining admixture demand caused by the pozzolan. 4. Increase in drying shrinkage of mortar bars dried 28 days. This limit is applied only at the request of the purchaser to show whether the pozzolan will cause a substantial increase in shrinkage in mortar bars. 5. Reactivity with cement alkalies. Optional mortar-bar expansion tests (ASTM C 44) can be requested if pozzolan is to be used with an aggregate regarded as deleteriously reactive with cement alkalies. 6. Sulfate expansion. Optional test for sulfate deterioration (ASTM C 1012) can be requested when the concrete will be exposed to sulfate environments. 3.4--General specification provisions ASTM C 618 requires that the purchaser or a representative have access to stored natural pozzolan for the purpose of inspection and sampling and that natural pozzolan may be rejected if it fails to meet any of the specified requirements. 3.5--Methods of sampling and testing ASTM C 311 outlines the procedures to be used for verification of pozzolan characteristics. For a number of test procedures, reference is made to other cement, mortar, or concrete tests for the body of the test procedure with ASTM C 311, indicating the modifications in proportions, preparation procedures, or test parameters needed to accommodate the testing. The three main divisions of the standard are sampling methods, chemical analysis methods, and physical test procedures. Either individual grab samples or composite samples may be used depending on the circumstances. The method provides detailed procedures for sampling from: (1) conveyor delivering to bulk storage; (2) bulk storage at points of discharge; (3) bulk storage by means of sampling tubes; and (4) railroad cars or trucks. Chemical analysis procedures involve determining moisture content by drying to constant weight and then the loss of ignition. The latter requires

igniting the dried sample to constant weight in a muffle furnace at 750 [plus/minus] 50 C using an uncovered porcelain crucible (not platinum crucible as used for cement testing). Many of the required chemical determinations are then made using procedures that are the same as, or very similar to, those used in testing portland cement. Physical tests include the determining of specific gravity and the amount retained on the 45-m (No. 325) sieve using the test methods developed for portland cement. Soundness and strength testing procedures are included in ASTM C 311 with reference to cement testing procedures where appropriate. 3.6--Quality control and quality assurance The first recommended step in starting a pozzolan quality control program is to establish the quality history for each source of pozzolan. This quality history should include ASTM C 618 certification as well as at least 40 individual test results for loss on ignition, amount retained on the 45-A. (No. 325) sieve, specific gravity, and SO+3, content. The purpose of the quality history is to demonstrate that the pozzolan consistently conforms to specification and uniformity requirements. An analysis of these data by statistical techniques helps to determine whether the source of pozzolan is suitable for the intended use. A company selling natural pozzolan intended to be in conformance with ASTM C 618 should have a quality control program that is technically and statistically sound. After the quality history is established, the source must be retested to assure continued conformance to ASTM C 618. The important characteristics of the particular source of a pozzolan should be determined and a quality control program established for that source, taking into account those characteristics and the requirements of specifications for its use in concrete. Samples may also be taken periodically and stored in the event that future testing and evaluation is desirable. ASTM C 311 provides for tests to be conducted on natural pozzolan samples representing not more than 440 Mg (400 tons) for certain tests and not more than 2200 Mg (2000 tons) for others. Sampling and testing on a time-schedule basis, in addition the to the tonnage basis prescribed by ASTM C 311, may be a useful part of the program. An effective quality control program allows the supplier to maintain test reports for demonstration of product compliance with regard to the physical, chemical, and variability requirements of ASTM or other special project performance requirements as well as to monitor variability of critical characteristics. Statistical evaluations of the test data provide the supplier with information on long-term variations. In addition to the producer's quality-control program, some users have extensive quality assurance programs, for example that of the US Army Corps of Engineers for US government projects. CHAPTER 4--CONCRETE PRODUCTION WITH NATURAL POZZOLANS 4.1--Storage Since natural pozzolans are normally of lower density than portland cement, bulk unit weight should be considered when ordering or taking inventory. The bulk unit weight in bins or silos is generally assumed to be between 880 and 1280 kg/m.3- (55 and 80 lb/ft.3-); whereas cement in bins and

silos is generally assumed to be between 960 and 1500 kg/m.3- (60 and 94 lb/ft.3-). Both pozzolan and cement may have lower bulk density immediately after conveying (Strehlow 1973). Bulk pneumatic tank trucks that typically carry cement and pozzolan are usually large enough in volume to receive a full, legal load for over-highway delivery. Pozzolan of very low bulk density will reduce the load that can be carried. Bins and silos intended for cement may be used to store pozzolan. They should be large enough to receive at least two deliveries. Due to the similar appearance of pozzolan and cement, it is prudent to color-code and label the fill pipes or to take other precautions to minimize the possibility of cross-contamination. Care must also be taken to clearly identify which storage compartments contain pozzolan and to establish proper materials management procedures (Gaynor 1978). Bins should be completely cleaned out when they are being switched over to handle a different type of material. As with cement from different mills, pozzolan from different sources should not be mixed in the same bin. Pozzolan flows readily when aerated. This characteristic increases the possibility of leakage from bins and silos. When cement and pozzolan must be stored in different compartments of the same bin or silo and are separated by a dividing partition, frequent inspections of the partition must be made. A double wall with an intervening air space is highly recommended; otherwise, pozzolan may move from one bin to the other through faulty welded connections, or through holes caused by wear. Since it is virtually impossible to detect contamination of a cement storage compartment by visually examining the cement as batches of the concrete are mixed, care in avoiding intermingling of cement and pozzolan is of great importance. A separate silo for pozzolan is preferred. Each storage bin and silo should be equipped with a positive shutoff to control the flow of the pozzolan in the weigh batcher. Rotary valves, rotary valve feeders, and butterfly valves are generally suitable for this purpose. A conventional scissor gate may be used if it is well maintained. Independent dust collectors on cement and pozzolan bins are recommended. 4.2--Batching When batching pozzolan and cement at a concrete plant, it is not necessary to install separate weigh batchers. Pozzolan and cement may be weighed cumulatively in the same weigh batcher. Cement normally should be weighed first so that accidental overbatching of pozzolan will not cause underbatching of cement (Gaynor 1978). To transport pozzolan from bin to weigh batcher, methods such as gravity flow, pneumatic or screw conveyors, or air slides are most often used. The method depends on the location of the pozzolan bin relative to the weigh hopper. Pozzolan from overhead storage is normally conveyed by gravity flow or an air slide. If the pozzolan storage is at nearly the same level as the weigh batcher, an air slide or a screw conveyor can be used. Since pozzolan flows very easily, a positive shut-off valve should be installed to insure that pozzolan does not flow through the air slide or screw when the conveying device is stopped. Pozzolan can be conveyed from lower level storage by pneumatic conveyor. 4.3--Mass concrete Mass concrete was one of the first types of concrete in which natural pozzolans or fly ash were used in the United States (ACI 207). Extensive data from tests and experience in the use of pozzolans are given by Davis (1950). Mather (1971) provided a review of their use in construction of concrete dams. Valuable reports on their use in mass concrete are given by

Davis (1963), Price and Higginson (1963), Waugh (1963), Kokubu (1963), and Tuthill, Adams, and Mitchell (1963). Elfert (1974) gives an extensive report on Bureau of Reclamation experience with fly ash and other pozzolans over the period of 1942 to 1973, with reference also to use of inert finely divided mineral admixtures in mass concrete in the period of 1915 to 1916. Today, there are few mass concrete dams built in any part of the world that do not contain natural pozzolans, fly ash, or ground slag in the concrete. By using natural pozzolan concrete in massive dam construction, it is possible to achieve a reduction of the temperature rise without incurring the undesirable effects associated with very lean mixtures; i.e., harshness, bleeding, tendency to segregate, and tendency to increased permeability (Price 1982). In addition, use of pozzolan can reduce the thermal stresses by the reduction of the heat of hydration in mass concrete structures (Blanks, Meissner, and Rawhauser 1938; Carlson, Houghton, and Polivka 1979). Improved sulfate resistance and reduction of alkali-aggregate reaction provided by proper incorporation of pozzolan into concrete mixtures are other important considerations in the construction of massive concrete dams. CHAPTER 5--NATURAL POZZOLANS IN CONCRETE PRODUCTS 5.1--Concrete masonry units Some manufacturers of concrete masonry units use as much as 35 percent pozzolan in the cementitious material for the autoclave manufacture of high-pressure steam-cured products. Others use from 15 to 35 percent in the cementitious material for the manufacture of low-pressure steam-cured products. Concrete obtains the necessary strength with improved finish and texture, better mold life, and sharper corners on the finished product when using natural pozzolans. Also, pozzolan reportedly gives added plasticity to the relatively harsh mixtures used in concrete masonry units (Belot 1967). Autoclave curing is not as commonly used as in the past, and some of the newer curing systems with short preset times can present early strength problems when pozzolans are used. When pozzolan is used in concrete products cured in an autoclave at temperatures of 135 to 190 C (275 to 374 F) and pressures of 0.52 to 1.17 MPa (75 to 170 psi), the cement content may be reduced by 30 to 35 percent. Concrete masonry units cured in high-pressure autoclaves show early strength equivalent to that of 28-day moist-cured strength and reduction in volume change in drying (Hope 1981). Particular care should be taken to insure that the pozzolan meets the soundness requirement of ASTM C 618. Typical cement replacement in low-pressure steam-curing applications averages about 20 percent pozzolan. Tests for resistance to freezing and thawing of concrete masonry units containing pozzolans indicate that such units could be expected to perform well in vertical wall construction. For the more severe condition of horizontal exposure, a minimum compressive strength of 21 MPa (3000 psi) based upon the net area of the unit is recommended when normal weight aggregates are used. Air entrainment is not practical at the extremely low or zero slumps used for concrete block. It could be applicable to slump block or quarry tile. To provide adequate resistance to freezing and thawing for units made with concrete having appreciable slump, air entrainment is needed (Redmond 1969). When proportioning mixtures, concrete product producers should check the grading and types of aggregates, cements, equipment, and kiln

temperatures, and then adjust trial batches with various amounts of pozzolans to achieve specific technical or economic objectives (Valore 1970). Pozzolan can be used to reduce moisture absorption of masonry units. 5.2--Concrete pipes Pozzolans may provide significant benefits in the manufacture of concrete pipes. Properly proportioned mixtures containing pozzolans make the concrete less permeable, and pipe may be more resistant to weak acids and sulfates (Davis 1954; K. Mather 1982). The increase in sulfate resistance achieved is dependent upon the type of cement, type of pozzolan, bedding and backfill used, the ground water, and the sulfate concentration. Many concrete pipe producers use cement contents higher than needed for strength to obtain the required workability. In a packerhead pipe operation, concrete with a very dry consistency and low water content is compacted into a vertical pipe form using a revolving compaction tool. The cement content can be reduced by replacing some of the cement with pozzolan. Equipment used in pipe production (that is, wings and long bottoms) may last longer due to the lubrication effect. Use of a natural pozzolan can increase the cohesiveness of the no-slump, freshly placed concrete, facilitating early form stripping. A reduction in the heat of hydration of concrete mixtures containing pozzolan can reduce the amount of hairline cracks on the inside surface of stored pipe sections (Cain 1979) and concrete mixtures containing pozzolan tend to bleed less. 5.3--Prestressed concrete products Each form used in the production of prestressed concrete products requires a large capital investment. For this reason, prestressed concrete products generally achieve their competitive position in the marketplace by using a limited number of forms for their production and using a rather short production cycle. Production cycles of 10 to 12 hr are common. Compressive strengths of 24 to 28 MPa (3500 to 5000 psi) are required at the time of form removal or stripping to transfer the prestress forces from the form or prestressing bed to the concrete. The high compressive strengths at transfer are necessary to obtain good bond of the concrete to the prestressing steel, to control camber of the member, to control creep and shrinkage of the concrete, and to reduce prestress losses. These early concrete strengths are generally achieved with cement contents of 355 to 455 kg/m.3- (600 to 750 lb/yd.3-), conventional or high-range water-reducing admixtures or both, and curing methods employing elevated temperatures. A nonchloride accelerating admixture is sometimes used. Under these conditions, pozzolans are not generally used for prestressed concrete structural members, or prestressed concrete pipe. In general, natural pozzolans are more desirable for applications where early strength is not a critical parameter. This usually occurs only when the production backlog is low or when the specifications prohibit form removal before specified ages. When pozzolans are used, better surfaces with fewer air voids are usually achieved. This is attributed to the improved workability obtained by using them. Pozzolans are not known to have been used in prestressed concrete pipe. Specific tests to evaluate long-term resistance to corrosion of the reinforcing steel are needed before they can be recommended for this application. CHAPTER 6--OTHER USES OF NATURAL POZZOLANS 6.1--Grouts and mortars According to ACI 116R, grout is "a mixture of cementitious material and

water, with or without aggregate, proportioned to produce a pourable consistency without segregation of the constituents." Its primary purpose is to fill spaces or voids. Mortar contains the same basic ingredients, but with a less fluid consistency. Mortar used in masonry construction is specified by ASTM C 270. This specification permits the use of natural pozzolans as a blended cement. The benefits of using natural pozzolans in mortars have not been fully investigated; however, they may affect bond strength, time of set, and other important properties of mortar. The benefits derived from using natural pozzolan in grouts are economy, improved workability, lower heat of hydration, reduced alkali-silica reaction expansion, reduced permeability, and improved sulfate resistance. Common uses of grout include: (a) in preplaced aggregate concrete where grout is injected into the voids of previously placed coarse aggregate to produce concrete (ACI 304); (b) contact grouting either under machinery to fill the space between a base plate and the substrate concrete or between the top surface of concrete placed or pumped under existing concrete or rock, as in tunnel linings; (c) to provide support for deep mine applications; (d) in curtain grouting where very fluid mixtures (often with the aggregate omitted) are used to fill cracks or fissures in rock; (e) in soil and hazardous waste stabilization, to fill voids in the soil or between particles to decrease permeability, densify, and generally improve its load carrying capacity; (f) in slab jacking, to raise and realign concrete slabs or structures that have settled, and (g) in underwater placing and slope protection where grout is generally injected into preplaced, inflatable cloth bags or blankets that are flexible enough to conform to the surrounding contour to completely fill the void and provide complete contact. 6.2--Controlled low-strength materials Formulations containing pozzolan, cement, water, and fine aggregate have been used as controlled density fills in place of compacted soil. These formulations, delivered by truck mixers, can be proportioned to flow like a liquid, but they are capable of supporting normal loads after hardening. No tamping or compaction is necessary after placement to achieve strength. Such materials can be used for trench backfilling, pipe bedding, foundation subbase, paving subbase, floor fills, culvert backfill, and filling abandoned tanks, manholes, and sewer lines. The primary use of controlled low-strength materials is as a replacement for compacted granular materials where settlement could cause problems. Compressive strengths ranging from about 0.3 to 9.7 MPa (50 to 1200 psi) can be achieved, which provides the necessary rigidity for volume stability. At strength levels less than 1.03 MPa (150 psi), such formulations can be readily excavated. Economy is achieved because no backfill labor crews and equipment are necessary. The material can be self-leveling and can support normal loads in as little as 4 hr after pouring. However, the amount of bleed water that comes to the surface after placement of these very wet mixtures must be considered in some applications. Pozzolan can also be used as a fill material by itself. The necessary moisture requirements and packing densities can be determined through the use of laboratory and field tests. Work on this class of products is the responsibility of ACI Committee 229. CHAPTER 7--REFERENCES 7.1--Specified and/or recommended references The documents of the various standards-producing organizations referred to in this document are listed below with their serial designation. The documents listed were the latest in effect at the time this document was written. Since some of these documents are revised frequently, the user

should check directly with the sponsoring group if it is desired to refer to the latest revision. American Concrete Institute (ACI) 116R 201.2R 207 211.1 212.1R 212.2R 304R 308 318 SP-1 SP-46 SP-79 Cement and Concrete Terminology Guide to Durable Concrete Recommended Practice for Mass Concrete for Dams and Other Massive Structures Standard Practice for Selecting Proportions for Normal, Heavyweight, and Mass Concrete Admixtures for Concrete Guide for Use of Admixtures in Concrete Guide for Measuring, Mixing, Transporting and Placing Concrete Standard Practice for Curing Concrete Building Code Requirements Symposium on Mass Concrete 1963 Proportioning Concrete Mixes 1974 Fly Ash, Silica Fume, Slag and Other Mineral By-Products in Concrete, 2 volumes, 1983, V. M. Malhotra, Editor

American Society for Testing & Materials (ASTM) C 109 C C C C 150 151 185 227 Standard Test Method for Compressive Strength of Hydraulic Cement Mortars (Using 2-in. or 50-mm Cube Specimens). Standard Specification for Portland Cement Standard Test Method for Autoclave Expansion of Portland Cement Standard Test Method for Air Content of Hydraulic Cement Mortar Standard Test Method for Potential Alkali Reactivity of CementAggregate Standard Methods of Sampling and Testing Fly Ash or Natural Pozzolans for Use as a Mineral Admixture in Portland Cement Concrete Standard Test Method for Effectiveness of Mineral Admixtures in Preventing Excessive Expansion of Concrete due to the AlkaliAggregate Reaction Standard Specification for Blended Hydraulic Cements Standard Specification for Fly Ash and Raw or Calcined Natural Pozzolan for Use as a Mineral Admixture in Portland Cement Concrete Standard Test Method for Length Change of Hydraulic Cement Mortars Exposed to a Sulfate Solution

C 311 C 441 C 595 C 618 C 1012

Transportation Research Board "Admixtures in Concrete, Highway Research Board. Special Report 119, 32 pp. 1971; Washington, D.C. (Chapter 4, Pozzolans in Highway Concrete," pp 21-28, Report of Committee MC-B5). 7.2--Cited references Adams, R. F., 1968, "ASTM Standards and Concrete for the California Water Project," presented at 71st Annual ASTM Meeting, San Francisco, CA. Bates, P. H.; Phillips, A. J.; and Wig, R. J., 1912, "Action of the Salts in Alkali Water and Sea Water on Cements," Technologic Paper No. 12, National Bureau of Standards. Belot, J. R. Jr., 1967, "Fly Ash in Concrete Block Manufacturing," Proceedings, 1st Fly Ash Utilization Symposium (Pittsburgh, Mar.), Information Circular No. 8348, U.S. Bureau of Mines, Washington, D.C. Blanks, R. F.; Meissner, H. S.; and Rawhauser, C., 1938, "Cracking in

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CONVERSION FACTORS 1 mm = 0.039 in. 1 MPa = 145 psi 1 kg/m.3- = 0.06242 lb/ft.3-

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This report was submitted to letter ballot of the committee and was approved in accordance with Institute balloting procedures.